US4684671A - Energy beam curable composition - Google Patents

Energy beam curable composition Download PDF

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Publication number
US4684671A
US4684671A US06/855,310 US85531086A US4684671A US 4684671 A US4684671 A US 4684671A US 85531086 A US85531086 A US 85531086A US 4684671 A US4684671 A US 4684671A
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US
United States
Prior art keywords
group
compound
energy beam
aliphatic
represented
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US06/855,310
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English (en)
Inventor
Hiroshi Tsuchiya
Kazuhiko Morio
Hisashi Murase
Kazuo Ohkawa
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Adeka Corp
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Asahi Denka Kogyo KK
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Assigned to ASAHI DENKA KOGYO K.K. reassignment ASAHI DENKA KOGYO K.K. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: MORIO, KAZUHIKO, MURASE, HISASHI, OHKAWA, KAZUO, TSUCHIYA, HIROSHI
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G85/00—General processes for preparing compounds provided for in this subclass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/687—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/114—Initiator containing
    • Y10S430/122—Sulfur compound containing

Definitions

  • the present invention relates to a composition capable of curing upon irradiation with an energy beam. More particularly, it relates to a resin composition which, when used as a coating material, readily cures and affords a cured coating film which gives off very little odor and bleeds very little decomposition products induced by irradiation.
  • the composition containing an aromatic onium salt mentioned above is inferior in curability to the one containing a diazonium salt.
  • the aromatic onium salt is an aromatic sulfonium salt
  • the composition containing it gives off an ill-smelling low-molecular weight compound when irradiated with an energy beam, with the result that the coating film has a foul smell.
  • a high-molecular weight aromatic sulfonium salt having a specific group in Japanese Patent Laid-open No. 55420/1981. However, it still is not satisfactory although it eliminates the disadvantage to some extent. Upon irradiation, it forms a low-molecular weight compound such as bisphenyl sulfide, which remains in the coating film, causing the film to smell.
  • R 1 -R 10 are each a hydrogen atom, halogen atom, nitro group, alkoxy group, C 1 -C 18 aliphatic group, or C 6 -C 18 substituted or unsubstituted phenyl, phenoxy, or thiophenoxy group, with at least one of R 1 -R 10 being (A) a C 1 -C 18 aliphatic group having at least one hydroxyl group or (B) a C 3 -C 19 aliphatic group having a group of --OCH 2 CH 2 O--.);
  • Z is a group represented by the formula MQ l (III) or the formula MQ l-1 OH (IV). (where M denotes B, P, As, or Sb; Q denotes a halogen atom; and l is an integer of 4 to 6.)]
  • a cationically polymerizable substance to use in the invention includes epoxy resins, vinyl ethers, cyclic ethers and ketones, lactones, oxetanes, styrenes, acroleins, vinyl arenes (e.g., 4-vinylbiphenyl), alicyclic vinyl compounds (e.g., vinylcyclohexane), spiro-orthoesters, spiro-orthocarbonates, bicyclo-orthoesters, isobutylene, dienes (e.g., butadiene and isoprene), and phenol-formaldehyde resins. They are in the form of monomer or prepolymer. Preferable among them is epoxy resins.
  • the epoxy resins used in this invention are known aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins.
  • Preferred aromatic epoxy resins are a polyglycidyl ether derived from polyhydric phenol having at least one aromatic nucleus or alkylene oxide adduct thereof.
  • Their examples include glycidyl ether resins produced by the reaction between bisphenol A or alkylene oxide adduct thereof and epichlorohydrin, and they also include epoxy-novolac resins.
  • aromatic epoxy resins may be used individually as the cationically polymerizable substance in the the curable composition of this invention. However, they may be properly combined with one another according to the desired performance.
  • the onium salt of a Lewis acid which is the other essential constituent in this invention, is represented by the following formula. ##STR5## [where X is a sulfonio group represented by the following formula (II)]. ##STR6## R 1 -R 10 are independently selected from various kinds of groups excluding basic groups such as amino groups.
  • they are a hydrogen atom, halogen atom (e.g., F, Cl, Br, and I), nitro group, alkoxy group (e.g., CH 3 O-- and C 2 H 5 O--), C 1 -C 18 aliphatic group (e.g., hydrocarbon group such as CH 3 --, C 2 H 5 --, and (CH 3 ) 2 CH--; cyclic hydrocarbon group such as cyclohexyl group; and those which contain a hetero atom in the main chain or substituent group (e.g., ##STR7## --S--CH 3 , --O--CH 2 --CH 2 --OH, --O--CH 2 Ph, and or substituted or unsubstituted phenyl group, phenoxy group, or thiophenoxy group.
  • halogen atom e.g., F, Cl, Br, and I
  • alkoxy group e.g., CH 3 O-- and C 2 H 5 O--
  • At least one of R 1 -R 10 is (A) a C 1 -C 18 aliphatic group having at least one hydroxyl group or (B) a C 3 -C 19 aliphatic group having a group of --OCH 2 CH 2 O--.
  • the substituent group belonging to (A) includes monoalcohol and polyalcohol represented by, for example, --CH 2 OH, --CH 2 CH 2 OH, --O--CH 2 --CH 2 --CH 2 --CH 2 --OH, --SCH 2 CH 2 OH, ##STR8##
  • substituent groups belonging to (B) include --CH 2 O--CH 2 --CH 2 --O--CH 3 , ##STR9## --O--CH 2 CH 2 -- 2 OH, --O--CH 2 CH 2 -- 2 OCH 3 , and --OCH 2 CH 2 -- 3 OH.
  • R 1 to R 10 may be any of the substituent groups defined by (A) and (B). Where eight or nine of R 1 to R 10 are hydrogen atoms, R 3 and/or R 8 should be the substituent groups defined by (A) and (B), for the ease of synthesis.
  • Y in the above formula (I) is a group represented by the formula (II), or a hydrogen atom, halogen atom, nitro group, alkoxy group, C 1 -C 18 aliphatic group, C 6 -C 18 substituted or unsubstituted phenyl group, phenoxy group, or thiophenoxy group (which are all defined as above).
  • n is an integer of 1 to 3
  • m is an integer of 1 to 2.
  • Y is a sulfonio group represented by the formula (II)
  • m is 2.
  • Z is a group represented by the formula MQ l (III) or the formula MQ l-1 OH (IV).
  • M denotes B, P, As, or Sb
  • Q denotes a halogen atom (preferably Cl or F); and
  • l is an integer of 4 to 6.
  • Examples of Z include BF 4 , PF 6 , AsF 6 , SbF 6 , and SbF 5 OH.
  • the onium salt of a Lewis acid used in this invention may be synthesized by (i) the reaction to form a sulfonium salt from a starting material having the desired substituent group, or by (ii) synthesizing an adequate substituted or unsubstituted group sulfonium salt and subsequently converting or introducing the substituent group.
  • the curable composition of this invention is composed essentially of 100 wt. parts of a cationically polymerizable substance and 0.1 to 15 parts by weight, preferably 0.4 to 8 parts by weight, of the onium salt of Lewis acid represented by the formula (I).
  • the adequate ratio is determined according to the type and dosage of energy beam and other many factors such as desired cure time, temperature, humidity, and coating thickness.
  • the curable composition of this invention is a liquid having a viscosity of 1 to 100,000 centipoise at 25° C. or a solid soluble in a solvent. Upon irradiation of energy beam such as ultraviolet light, it becomes dry to touch or solvent-insoluble within a tenth of minute to several minutes.
  • energy beam such as ultraviolet light
  • the energy beam is not specifically limited so long as it has sufficient energy to induce the decomposition of an initiator.
  • the preferred energy beam is an electromagnetic wave energy beam having a wavelength of 2000 ⁇ to 7000 ⁇ produced by a high- or low-pressure mercury-vapor lamp, xenon lamp, bacteriocidal lamp, and laser; electron beam and X rays.
  • composition of this invention may be incorporated with a solvent for dilution and an inert resin or prepolymer for modification, so long as they do not adversely affect the cationic polymerization.
  • the composition may be incorporated with an organic carboxylic acid or acid anhydride for the improvement of electrical properties, or blended with a polyol or flexible prepolymer to impart rubbery resilience.
  • composition of this invention is usually a transparent liquid; and it may be incorporated with an inert pigment, dye, filler, antistatic agent, flame retardant, gelation inhibitor, flow regulator, surface active agent, adhesion improver, processing aid, viscosity adjustor, sensitizer, ultraviolet light absorber, and the like, according to the intended use.
  • the amount of these additives depends on the performance required and the curing characteristics.
  • composition of this invention can be applied to metal, wood, rubber, plastics, glass, and ceramics.
  • composition of this invention cures in a short time upon irradiation with an energy beam, and it passes into a cured product having good physical properties, forming very little amount of low molecular weight compound that causes an offensive odor and adversely affects the properties of the coating film.
  • Triphenylsulofonium-hexafluorophosphate compound 3
  • diphenyl-4-thiophenoxyphenylsulfonium-hexafluorophosphate compound 4
  • bis[4-(diphenylsulfonio)phenyl]sulfide-bishexafluorophosphate compound 5
  • the above-mentioned five compounds were examined for photodegradation in the following manner. Each compound was dissolved in a methanol-water mixture (1:9) to give a 2000 ppm solution. The solution was exposed to ultraviolet light emitted by four fluorescent lamps FL6E (6 W) (made by Sankyo Denki Co., Ltd.) placed 10 cm away, for 30 minutes. The low-molecular weight compounds formed by exposure were identified by gas chromatography. The column was Tenax GC (1 m), and the temperature was raised from 150° C. to 270° C. at a rate of 15° C./min. The results are shown in Table 1.
  • the decomposition products of Compound 1 were identified as bis(p-2-hydroxyethoxyphenyl)sulfide (about 20%) and bis(p-2-hydroxyethoxyphenyl)sulfoxide (about 5%). These compounds are all odorless solids.
  • the resulting mixture was applied to an aluminum test panel (in coating thickness of 10 ⁇ m), and the coating was irradiated with a high-pressure mercury-vapor lamp, whereby a cured coating was obtained.
  • the coating film was examined for elusion according to the method stipulated in the Food Sanitation Law (Notification No. 20 of the Ministry of Public Welfare, February 1982). The amount of residues on evaporation was measured. The results are shown in Table 2.
  • ERL-4221 alicyclic epoxy resin, made by Union Carbide Corp.
  • ERL-4221 alicyclic epoxy resin, made by Union Carbide Corp.
  • the resulting solution was applied to an aluminum test panel (in coating thickness of 5 ⁇ m), and the coating film was irradiated with a high-pressure mercury-vapor lamp (80 W/cm) placed 10 cm away.
  • the tack-free time time for the coating film to dry to touch was measured.
  • Table 3 The results are shown in Table 3.
  • the compositions were good in storage stability, with no increase in viscosity after storage at 40° C. for 3 months.
  • epoxy resin formulations 1 and 2 were prepared.
  • Formulation 1 80 parts of ERL-4221 and 20 parts of DY-022
  • Formulation 2 20 parts of ERL-4221, 60 parts of Ep-4100 (bisphenol A epoxy resin, made by Asahi Denka Co., Ltd.), and 20 parts of DY-022.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Epoxy Resins (AREA)
  • Paints Or Removers (AREA)
  • Polymerization Catalysts (AREA)
US06/855,310 1985-01-25 1986-03-18 Energy beam curable composition Expired - Lifetime US4684671A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP60012241A JPS61190524A (ja) 1985-01-25 1985-01-25 エネルギ−線硬化性組成物

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US4684671A true US4684671A (en) 1987-08-04

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US (1) US4684671A (enrdf_load_stackoverflow)
EP (1) EP0240582B1 (enrdf_load_stackoverflow)
JP (1) JPS61190524A (enrdf_load_stackoverflow)
WO (1) WO1993013139A1 (enrdf_load_stackoverflow)

Cited By (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4931337A (en) * 1987-02-12 1990-06-05 Canon Kabushiki Kaisha Information recording medium
US4940651A (en) * 1988-12-30 1990-07-10 International Business Machines Corporation Method for patterning cationic curable photoresist
US4954416A (en) * 1988-12-21 1990-09-04 Minnesota Mining And Manufacturing Company Tethered sulfonium salt photoinitiators for free radical polymerization
US5026624A (en) * 1989-03-03 1991-06-25 International Business Machines Corporation Composition for photo imaging
US5047568A (en) * 1988-11-18 1991-09-10 International Business Machines Corporation Sulfonium salts and use and preparation thereof
US5061605A (en) * 1990-04-17 1991-10-29 Fuji Photo Film Co., Ltd. Photopolymerizable composition containing photoinitiators having at least two sulfur atoms
US5158989A (en) * 1989-11-18 1992-10-27 Somar Corporation Electroless plating-resisting ink composition
US5166125A (en) * 1992-02-19 1992-11-24 Eastman Kodak Company Method of forming color filter array element with patternable overcoat layer
US5166126A (en) * 1992-02-19 1992-11-24 Eastman Kodak Company Color filter array element with protective overcoat layer and method of forming same
US5264325A (en) * 1988-12-30 1993-11-23 International Business Machines Corporation Composition for photo imaging
US5278010A (en) * 1989-03-03 1994-01-11 International Business Machines Corporation Composition for photo imaging
US5304457A (en) * 1989-03-03 1994-04-19 International Business Machines Corporation Composition for photo imaging
US5439779A (en) * 1993-02-22 1995-08-08 International Business Machines Corporation Aqueous soldermask
US5439766A (en) * 1988-12-30 1995-08-08 International Business Machines Corporation Composition for photo imaging
US5502083A (en) * 1993-06-18 1996-03-26 Nippon Kayaku Kabushiki Kaisha Onium salt, photopolymerization initiator, energy ray-curing composition containing the initiator, and cured product
US5550171A (en) * 1995-05-31 1996-08-27 International Business Machines Corporation Polymeric sulfonium salt photoinitiators
US5747223A (en) * 1988-12-30 1998-05-05 International Business Machines Corporation Composition for photoimaging
US5877229A (en) * 1995-07-26 1999-03-02 Lockheed Martin Energy Systems, Inc. High energy electron beam curing of epoxy resin systems incorporating cationic photoinitiators
US6051370A (en) * 1990-03-13 2000-04-18 Basf Aktiengesellschaft Radiation-sensitive mixture
US6180317B1 (en) 1988-12-30 2001-01-30 International Business Machines Corporation Composition for photoimaging
US20040242901A1 (en) * 2001-07-19 2004-12-02 Gabriele Norcini Sulfoniun salts, methods for their preparation and use thereof as phtoinitiators for radiation curable systems
US20050148679A1 (en) * 2003-12-29 2005-07-07 Chingfan Chiu Aryl sulfonium salt, polymerizable composition and polymerization method of the same
US20110300482A1 (en) * 2009-02-20 2011-12-08 San-Apro, Ltd Sulfonium salt, photo-acid generator, and photosensitive resin composition
US20160238767A1 (en) * 2013-09-30 2016-08-18 Lg Chem, Ltd. Polarizing plate, method for manufacturing same, and image display device comprising same

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08239623A (ja) * 1995-02-28 1996-09-17 Toagosei Co Ltd 木材用活性エネルギー線硬化型塗料組成物
JP2019137727A (ja) * 2018-02-06 2019-08-22 株式会社Adeka コーティング組成物
KR102792755B1 (ko) 2020-08-05 2025-04-07 산아프로 가부시키가이샤 광산 발생제

Citations (12)

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US2807648A (en) * 1955-09-16 1957-09-24 Stauffer Chemical Co Process for making sulfonium compounds
US4026705A (en) * 1975-05-02 1977-05-31 General Electric Company Photocurable compositions and methods
GB1516511A (en) * 1974-05-02 1978-07-05 Gen Electric Curable epoxide compositions
GB1516351A (en) * 1974-05-02 1978-07-05 Gen Electric Curable epoxide compositions
US4166478A (en) * 1977-12-21 1979-09-04 Kazuo Sugimura Accumulator having a bladder to be filled with liquid
US4173476A (en) * 1978-02-08 1979-11-06 Minnesota Mining And Manufacturing Company Complex salt photoinitiator
US4193799A (en) * 1976-07-09 1980-03-18 General Electric Company Method of making printing plates and printed circuit
US4231951A (en) * 1978-02-08 1980-11-04 Minnesota Mining And Manufacturing Company Complex salt photoinitiator
GB2061280A (en) * 1979-09-28 1981-05-13 Gen Electric Photopolymerisation using Triaryl Sulphonium Salts as Catalysts
US4291114A (en) * 1978-10-18 1981-09-22 Minnesota Mining And Manufacturing Co. Imageable, composite-dry transfer sheet and process of using same
US4374066A (en) * 1979-09-28 1983-02-15 General Electric Company Method for making triarylsulfonium salts
US4544732A (en) * 1984-12-24 1985-10-01 Shell Oil Company Heat-curable composition

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GB8330692D0 (en) * 1983-11-17 1983-12-29 Sericol Group Ltd Preparation of photoinitiators

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2807648A (en) * 1955-09-16 1957-09-24 Stauffer Chemical Co Process for making sulfonium compounds
GB1516511A (en) * 1974-05-02 1978-07-05 Gen Electric Curable epoxide compositions
GB1516351A (en) * 1974-05-02 1978-07-05 Gen Electric Curable epoxide compositions
GB1516352A (en) * 1974-05-02 1978-07-05 Gen Electric Halonium salts
US4026705A (en) * 1975-05-02 1977-05-31 General Electric Company Photocurable compositions and methods
US4193799A (en) * 1976-07-09 1980-03-18 General Electric Company Method of making printing plates and printed circuit
US4166478A (en) * 1977-12-21 1979-09-04 Kazuo Sugimura Accumulator having a bladder to be filled with liquid
US4173476A (en) * 1978-02-08 1979-11-06 Minnesota Mining And Manufacturing Company Complex salt photoinitiator
US4231951A (en) * 1978-02-08 1980-11-04 Minnesota Mining And Manufacturing Company Complex salt photoinitiator
US4291114A (en) * 1978-10-18 1981-09-22 Minnesota Mining And Manufacturing Co. Imageable, composite-dry transfer sheet and process of using same
GB2061280A (en) * 1979-09-28 1981-05-13 Gen Electric Photopolymerisation using Triaryl Sulphonium Salts as Catalysts
US4374066A (en) * 1979-09-28 1983-02-15 General Electric Company Method for making triarylsulfonium salts
US4544732A (en) * 1984-12-24 1985-10-01 Shell Oil Company Heat-curable composition

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4931337A (en) * 1987-02-12 1990-06-05 Canon Kabushiki Kaisha Information recording medium
US5047568A (en) * 1988-11-18 1991-09-10 International Business Machines Corporation Sulfonium salts and use and preparation thereof
US4954416A (en) * 1988-12-21 1990-09-04 Minnesota Mining And Manufacturing Company Tethered sulfonium salt photoinitiators for free radical polymerization
US6180317B1 (en) 1988-12-30 2001-01-30 International Business Machines Corporation Composition for photoimaging
US4940651A (en) * 1988-12-30 1990-07-10 International Business Machines Corporation Method for patterning cationic curable photoresist
US5747223A (en) * 1988-12-30 1998-05-05 International Business Machines Corporation Composition for photoimaging
US5439766A (en) * 1988-12-30 1995-08-08 International Business Machines Corporation Composition for photo imaging
US5264325A (en) * 1988-12-30 1993-11-23 International Business Machines Corporation Composition for photo imaging
US5026624A (en) * 1989-03-03 1991-06-25 International Business Machines Corporation Composition for photo imaging
US5278010A (en) * 1989-03-03 1994-01-11 International Business Machines Corporation Composition for photo imaging
US5304457A (en) * 1989-03-03 1994-04-19 International Business Machines Corporation Composition for photo imaging
US5158989A (en) * 1989-11-18 1992-10-27 Somar Corporation Electroless plating-resisting ink composition
US6051370A (en) * 1990-03-13 2000-04-18 Basf Aktiengesellschaft Radiation-sensitive mixture
US5061605A (en) * 1990-04-17 1991-10-29 Fuji Photo Film Co., Ltd. Photopolymerizable composition containing photoinitiators having at least two sulfur atoms
US5166125A (en) * 1992-02-19 1992-11-24 Eastman Kodak Company Method of forming color filter array element with patternable overcoat layer
US5166126A (en) * 1992-02-19 1992-11-24 Eastman Kodak Company Color filter array element with protective overcoat layer and method of forming same
US5439779A (en) * 1993-02-22 1995-08-08 International Business Machines Corporation Aqueous soldermask
US5502083A (en) * 1993-06-18 1996-03-26 Nippon Kayaku Kabushiki Kaisha Onium salt, photopolymerization initiator, energy ray-curing composition containing the initiator, and cured product
US5534557A (en) * 1993-06-18 1996-07-09 Nippon Kayaku Kabushiki Kaisha Onium salt, photopolymerization initiator, energy ray-curing composition containing the initiator, and cured product
US5629355A (en) * 1995-05-31 1997-05-13 International Business Machines Corporation Polymeric sulfonium salt photoinitiators
US5550171A (en) * 1995-05-31 1996-08-27 International Business Machines Corporation Polymeric sulfonium salt photoinitiators
US5877229A (en) * 1995-07-26 1999-03-02 Lockheed Martin Energy Systems, Inc. High energy electron beam curing of epoxy resin systems incorporating cationic photoinitiators
US20040242901A1 (en) * 2001-07-19 2004-12-02 Gabriele Norcini Sulfoniun salts, methods for their preparation and use thereof as phtoinitiators for radiation curable systems
US7230121B2 (en) 2001-07-19 2007-06-12 Lamberti Spa Sulfoniun salts, methods for their preparation and use thereof as photoinitiators for radiation curable systems
US20050148679A1 (en) * 2003-12-29 2005-07-07 Chingfan Chiu Aryl sulfonium salt, polymerizable composition and polymerization method of the same
US20110300482A1 (en) * 2009-02-20 2011-12-08 San-Apro, Ltd Sulfonium salt, photo-acid generator, and photosensitive resin composition
US8617787B2 (en) * 2009-02-20 2013-12-31 San-Apro, Ltd. Sulfonium salt, photo-acid generator, and photosensitive resin composition
US20160238767A1 (en) * 2013-09-30 2016-08-18 Lg Chem, Ltd. Polarizing plate, method for manufacturing same, and image display device comprising same
US10132976B2 (en) * 2013-09-30 2018-11-20 Lg Chem, Ltd. Polarizing plate, method for manufacturing same, and image display device comprising same

Also Published As

Publication number Publication date
JPH0456850B2 (enrdf_load_stackoverflow) 1992-09-09
EP0240582A1 (en) 1987-10-14
EP0240582B1 (en) 1990-07-04
WO1993013139A1 (en) 1993-07-08
JPS61190524A (ja) 1986-08-25

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